CN1492889A - Molded material comprising thermoplastic polyurethane consisting of ether-containing polyester polyol and method thereof and product therethrough - Google Patents
Molded material comprising thermoplastic polyurethane consisting of ether-containing polyester polyol and method thereof and product therethrough Download PDFInfo
- Publication number
- CN1492889A CN1492889A CNA018229336A CN01822933A CN1492889A CN 1492889 A CN1492889 A CN 1492889A CN A018229336 A CNA018229336 A CN A018229336A CN 01822933 A CN01822933 A CN 01822933A CN 1492889 A CN1492889 A CN 1492889A
- Authority
- CN
- China
- Prior art keywords
- ether
- polyester polyol
- weight parts
- containing polyester
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0895—Manufacture of polymers by continuous processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2290/00—Compositions for creating anti-fogging
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Disclosed is a thermoplastic polyurethane for slash molding, excellent in moldability, capable of providing a skin material having a uniform thickness, and capable of allowing a minute laser processing or the like to be vehicleried out thereon. Also, the present invention discloses a skin material comprising the thermoplastic polyurethane. The thermoplastic polyurethane of the present invention is prepared in a form of a powdery resin by mixing and then condensing an amount of 15-60 parts by weight of one or more isocyanate compounds; an amount of 30-70 parts by weight of an ether-containing polyester polyol; and an amount of 5-40 parts by weight of one or more chain extenders.
Description
Technical field
The present invention relates generally to moulding material, it contains the thermoplastic polyurethanes of being made up of ether-containing polyester polyol.More particularly, the present invention relates to have the moulding material of improving production quality, for example design flexible, embossing quality and texture; Weather resistance is scrape resistant, heat-proof aging, fast light and chemical resistant properties for example; And security feature for example anti-fog performance, flame retardant properties and can make the even inflation of air bag, it is used for fascia by containing the thermoplastic polyurethanes acquisition of being made up of ether-containing polyester polyol as skin-material.
Prior art
Usually, the skin-material of fascia need that excellent design is flexible, quality producies such as embossing quality and texture; And the weather resistance of excellent scrape resistant, heat-proof aging, fast light and chemically-resistant; And excellent anti-fog performance, flame retardant properties and can make the evenly security feature of inflation etc. of air bag.In this point, polyvinyl chloride (PVC) has excellent performance and satisfies such requirement, is widely used by vacuum forming, powder slush molding (PSM) etc.
Dashboard is divided into insert type substantially, combines with dashboard as the polyurethane(s) of cushioning material, and non-insert type, it is formed by injection-molded.
Insert type is made up of core, cushioning material and skin-material.Core is by the material manufacturing with excellent mechanical and physicals, and for example polypropylene is filled material (PPF) or PC/ABS, provides physical strength as the part of the core in the moulding material and to moulding material.In addition, cushioning material mainly is vibrating absorption material such as polyurethane foam, to absorb outside impact, is wrapped in simultaneously in the skin-material so that soft texture to be provided.As mentioned above, skin-material, the outer surface that it forms moulding material is the part that directly contacts user's skin, and provides improved aesthetic effect and texture according to design.
The insert type skin-material is usually by vacuum forming or the preparation of slush molding (PSM) method.Vacuum-formed skin-material obtains like this: by the flaky resin that heating under the vacuum is extruded in advance, the resin of heating is poured in the mould, cooled off the resin that forms, remove the resin of molding then from mould.On the other hand, the PSM method comprises mould that shakes and rotate heating at high temperature simultaneously and the container that contains toner, and with molten resin powder in mould, cooling frame is with the resin of solidification of molten.Compare with vacuum forming, the advantage of PSM method is to embody fully design and embossing feature.Based on such reason, the PSM method is mainly used in the dashboard of preparation limousine.
Calendar year 2001 is researched and analysed 77 types the skin-material that is used for fascia in the North America, find that polyvinyl chloride (PVC) by PSM method and vacuum moulding method molding is the material of the most frequent use.
But, by the poor heat resistance of the PVC of PSM and vacuum method preparation, be difficult to be applied to be contained in air bag in the automobile, and when burning, make the generation dioxin as internal part, therefore limited its application.Therefore, press for for example dashboard of a kind of moulding material of exploitation, comprise to be reused and to have improved texture and stable on heating new skin-material.
Disclosure of the Invention
Therefore the purpose of this invention is to provide a kind of moulding material, have the improved products quality, for example design flexible, embossing quality and texture; Weather resistance is scrape resistant, heat-proof aging, fast light and chemical resistant properties for example; And security feature for example anti-fog performance, flame retardant properties and air bag is evenly inflated, it is used for the dashboard of automobile by containing the thermoplastic polyurethanes acquisition of being made up of ether-containing polyester polyol as skin-material.
Implement optimal mode of the present invention
According to the present invention, a kind of moulding material is provided, comprise the thermoplastic polyurethanes of forming by the polyester polyol that contains ether, form by core, cushioning material and skin-material.Skin-material is by mixing one or more isocyanate compounds of 15～60 weight parts, one or more chain extension agents of the ether-containing polyester polyol of 30～70 weight parts and 5～40 weight parts, thereby the mixture that obtains of condensation is prepared then, wherein said isocyanate compound is selected from diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and dicyclohexyl methane diisocyanate (H12MDI), described chain extension agent is selected from polyvalent alcohol, and the example of enumerating is an ethylene glycol, glycol ether, butyleneglycol or hexylene glycol, trivalent alcohol is TriMethylolPropane(TMP) and poly-butyl ether glycol for example.
The polyester polyol that contains ether prepares as follows: mix one or more polyfunctional group carrier acid (vehicleboxylic) of 40～80 weight parts, the poly-butyl ether glycol (PTMG) of 20～100 weight parts, make the mixture reaction that obtains then, the hydroxyl value that obtains thus is 224.11～11.22mgKOH/g, the described carrier acid diacid of selecting oneself, pimelic acid (sbelicacid), suberic acid (abelic acid), nonane diacid, sebacic acid, dodecanedioic acid and trimer acid, described PTMG contains one or more multi-group alcohols, the hydroxyl value that has is 561.0～56.1mgKOH/g, be selected from glycol, the example of enumerating is an ethylene glycol, butyleneglycol or hexylene glycol and trivalent alcohol be TriMethylolPropane(TMP) for example.
Embodiment
According to the present invention, a kind of moulding material is provided, comprise the thermoplastic polyurethanes of forming by ether-containing polyester polyol, form by core, cushioning material and skin-material.Skin-material is by mixing one or more isocyanate compounds of 15～60 weight parts, one or more chain extension agents of the ether-containing polyester polyol of 30～70 weight parts and 5～40 weight parts, thereby the mixture that obtains of condensation is prepared then, wherein said isocyanate compound is selected from diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and dicyclohexyl methane diisocyanate (H12MDI), described chain extension agent is selected from glycol, and the example of enumerating is an ethylene glycol, glycol ether, butyleneglycol or hexylene glycol, trivalent alcohol is TriMethylolPropane(TMP) and poly-butyl ether glycol for example.
The thermoplastic polyurethanes that comprises ether-containing polyester polyol prepares as follows: mix one or more polyfunctional group carrier acid of 40～80 weight parts, the poly-butyl ether glycol (PTMG) of 20～100 weight parts, make the mixture reaction that obtains then, the hydroxyl value that obtains thus is 224.11～11.22mgKOH/g, the described carrier acid diacid of selecting oneself, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid and trimer acid, described PTMG contains one or more multi-group alcohols, the hydroxyl value that has is 561.0～56.1mgKOH/g, be selected from glycol, the example of enumerating is an ethylene glycol, butyleneglycol or hexylene glycol and trivalent alcohol be TriMethylolPropane(TMP) for example.
Be used for isocyanate compound of the present invention and can comprise the isocyanate compound that uses at the preparation polyurethane(s) usually, wherein common isocyanate compound can adopt with the conventional identical or similar mode of using method and use, be preferably selected from aromatic diisocyanate, aliphatic vulcabond, alicyclic diisocyanate, more preferably, be selected from diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and the dicyclohexyl methane diisocyanate (H12MDI) one or more.
Ether-containing polyester polyol prepares as follows: mix one or more polyfunctional group carrier acid of 40～80 weight parts, the poly-butyl ether glycol (PTMG) of 20～100 weight parts, make the mixture reaction that obtains then, the hydroxyl value that obtains thus is 224.11～11.22 mgKOH/g, the described carrier acid diacid of selecting oneself, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid and trimer acid, described PTMG contains one or more multi-group alcohols, the hydroxyl value that has is 561.0～56.1mgKOH/g, be selected from glycol, the example of enumerating is an ethylene glycol, butyleneglycol or hexylene glycol and trivalent alcohol be TriMethylolPropane(TMP) for example.
In embodiments of the present invention, the polyester polyol that contains ether can prepare as follows: mix multi-functional carrier acid, polyfunctional group alkylol cpd and poly-butyl ether glycol, mixture is heated to 140～160 ℃ from room temperature, the mixture of this heating of maintenance under 150 ℃ is about 60～120 minutes then, temperature is increased to 210～230 ℃ from 150 ℃, at 220 ℃ this mixture was kept about 10～120 minutes then, at 220 ℃, make the mixture reaction that obtains under the vacuum of 650～760mmHg, stopped reaction when hydroxyl value is lower than 1mgKOH/g, therefore the hydroxyl value that obtains is 224.11～11.22mgKOH/g.
Chain propagation agent can be selected from glycol, and the example of enumerating is ethylene glycol, glycol ether, butyleneglycol or hexylene glycol, trivalent alcohol for example TriMethylolPropane(TMP) and poly-butyl ether glycol (PTMG) or its mixture.
Thermoplastic polyurethanes comprises ether-containing polyester polyol, can prepare as follows: mainly be the ether-containing polyester polyol that mixes 30～70 weight parts, the chain propagation agent of 5～40 weight parts, stirred 1～10 minute down at 30～100 ℃; The isocyanic ester of 15～60 weight parts is added in first mixture, mix the mixture obtain subsequently simultaneously 300～1,100rpm stirred 1～10 minute down, in 60～140 ℃ of following slaking second mixtures 1～48 hour; Be lower than the reactant that efflorescence obtains from maturation stage under 0 ℃ the temperature; Reach and under 150～300 ℃, extrude the atomizing mixture.
In the first mixture step, polyol compound and chain propagation agent mainly are that homogeneous mixes, and at second mixing step, isocyanic ester and ether-containing polyester polyol mix to produce polyurethane(s).
In an embodiment of the invention, find that isocyanate compound and ether-containing polyester polyol are rapid at the mixing afterreaction.Specifically, the molecular weight of polyurethane(s) can be controlled by the maturation stage of the polyurethane(s) that obtains from second mixing step.Efflorescence step and extrusion step can make polyurethane(s) have suitable size.By efflorescence and maturation stage, polyurethane(s) forms the pellet that can be processed into goods.
Embodiment with reference to following will explain the present invention in more detail.But the following embodiment that provides only is used to illustrate the present invention, and the present invention is not limited by them.
Embodiment 1
At 1 of the hexanodioic acid that mixes 49.6kg, 22.0kg, 4-butyleneglycol and hydroxyl value are heated to 150 ℃ with mixture from room temperature after being the poly-butyl ether glycol of 448.8mgKOH/g, keep about 90 minutes down at 150 ℃, further be heated to 220 ℃ then, kept about 30 minutes down at 220 ℃.Then, the mixture of heating reacts under the vacuum of 720mmHg, and termination reaction when the hydroxyl value of mixture is lower than 1mgKOH/g obtains the condensation number and be 12.29, hydroxyl value is the ether-containing polyester polyol of 74.8mgKOH/g.Afterwards, 61kg ether-containing polyester polyol and 6kg1, the 4-butyleneglycol stirred 3 minutes simultaneously 60 ℃ of following mixing.After the 43kg hexamethylene diisocyanate joined in the mixture, the mixture that obtains mixed under 500rpm 3 minutes, therefore obtained condensation mixture.Then, condensation mixture was 80 ℃ of following slakings 8 hours.Subsequently, to form scale, the atomizing scale is extruded under 180 ℃ so that it forms pellet at the condensation mixture that is lower than efflorescence slaking under 0 ℃ the temperature.Use the pellet of thermoplastic polyurethanes, the PSM method of knowing according to prior art prepares the layered product of being made up of core, cushioning material and skin-material, and the part of moulding material is as the test materials of following tentative embodiment.
The comparative example 1～4
In comparative example 1～4, the part of commercial obtainable dashboard is as test materials.
In comparative example 1, use Hanwha Living ﹠amp; The polyvinyl chloride of Creative Corp.Korea is as skin-material, according to the part of the moulding material of PSM method preparation as test materials.In comparative example 2, use LG Chem.Ltd., according to vacuum forming method, the part of the layered product of preparation is as experiment material as skin-material for polyvinyl chloride/ABS resin of Korea (acrylonitrile-butadiene-styrene copolymer).In comparative example 3, use LG Chem.Ltd., the TPO of Korea is as skin-material, according to the part of the layered product of vacuum forming method preparation as experiment material.In comparative example 4, comprise Bayer Company, the polyester of USA as the part of the layered product of skin-material as experiment material.
Embodiment 1: the determining of proportion
In this test, estimate the proportion of each sample by the alternative method under water of definition in ASTM D 792.The results are shown in the following table 1.
Embodiment 2: the determining of tensile strength
By the method for the 3rd section of definition among the JIS K 6301, use MTS Company, the 1-ton Universal Test Equipment of USA is measured the tensile strength of each sample.The results are shown in the following table 1, the sample that wherein stretches is a 1-type dumbbell, and draw speed is 200mm/min.
Embodiment 3: the determining of surface hardness
Under initial compressed state, use A-type Shore scleroscope to estimate surface hardness according to the method for definition among the ASTM D 2240.The results are shown in the following table 1.
Embodiment 4: the scratch resistance evaluation
By 300g weight is placed on the sheet, according to the method among the SUS403, when swiping the experiment slice that once prepares, by observing the ocular estimate scratch resistance on top layer.According to the scratch degree that forms on the top layer, the evaluation of top layer outward appearance is divided into 5 grades, and is discernible from 1 grade of 5 grade of not damaging to the top layer of remarkable damage are arranged.The results are shown in the following table 1.
Embodiment 5: shock test
(General research Inc.Ltd., C02D USA) carry out the high speed impact experiment of skin-material in-30 ℃ ethanol bath to use drop weight shock-testing machine Dynatup.At room temperature estimate the skin-material (embodiment 1 and comparative example 3) that is combined with the polyurethane(s) cushioning material.The results are shown in Table 1, the nose heave 11.83kg in the right angle of trier wherein, and impact velocity and striking energy are respectively 6m/ second and 102J, and the diameter that impacts rod is 13mm.
Embodiment 6: the evaluation of heat-resistant aging
Use the chamber of fixed temperature and humidity to estimate heat aging property down in aging 500 hours, use colorimeter to measure aberration at 120 ℃.The results are shown in Table 1.
Embodiment 7: sunproof evaluation
Use the fast light experimental installation that quickens, Atlas Ci 65 Xenon Arc Weather O-meter are that 340nm, light intensity are 53W/m at phase wavelength
2And temperature is to carry out 500 hours under 89 ℃ the condition, and the colour-change of observation sample is estimated photostabilization.
Table 1
| ??E.1 | ????C.E.1 | ????C.E.2 | ????C.E.3 | ????C.E.4 | ||
| Proportion | ??1.13 | ????1.20 | ????1.28 | ????0.92 | ????1.08 | |
| Tensile strength (kgf/km) | ??66 | ????122 | ????148 | ????100 | ????70 | |
| Surface hardness (Shore A) | ??64 | ????78 | ????94 | ????76 | ????78 | |
| Scratch resistance | ??4 | ????5 | ????5 | ????5 | ????5 | |
| Impact property | Skin-material | ??6.2 | ????12.0 | ????12.1 | ????7.8 | ????12.8 |
| Skin-material + | ??6.8 | ????- | ????- | ????8.0 | ????- | |
| Heat-resistant aging | Skin-material | ??1.5 | ????0.4 | ????0.4 | ????1.2 | ????2.8 |
| Skin-material + | ??1.5 | ????1.0 | ????1.3 | ????1.1 | ????3.1 | |
| Photostabilization | Skin-material | ??1.1 | ????1.2 | ????0.4 | ????0.4 | ????0.2 |
| Skin-material + | ??0.7 | ????0.8 | ????0.9 | ????0.7 | ????0.7 | |
As table 1 signal, the moulding material of above-mentioned comparative example's 2 preparations is because the physical properties of the skin-material that wherein contains has minimum proportion.Because than using conventional comparative example 1 and 2 moulding materials that prepare to have lower proportion, according to the moulding material high approximately 6～10% of the embodiment of the invention 1 preparation with skin-material.In addition, the moulding material of embodiment 1 has similar comparative example's 4 proportion, shows that it can be applicable to automobile.By weight loss effect, skin-material of the present invention can provide acceleration characteristics, manipulation and the fuel efficiency of improved motor vehicle.
For tensile strength, find that the moulding materials of comparative example 1 and 2 preparations have relative high fracture tensile strength, and very low according to the tensile strength of the moulding material of embodiments of the invention 1 preparation.When preparing moulding material by PSM method rather than vacuum forming method, thermoplastic polyurethanes does not need high tensile strength.The bursting strength of considering laser scribing place when guaranteeing airbag deployment is that low-level, low tensile strength is favourable, can guarantee high airbag deployment performance like this.
Hardness for the top layer, the moulding material that discovery prepares in comparative example 2 has the highest surface hardness, comparative example 1,3 and 4 surface hardness are similar each other, and the moulding material of embodiment 1 preparation has minimum surface hardness, shows that moulding material prepared in accordance with the present invention has excellent sense of touch.
Typically, low hardness is with low scratch resistance.For scratch resistance, the moulding material for preparing according to the embodiment of the invention 1 is evaluated as 4 grades, wherein observes slight top layer damage, therefore satisfies Korea S's domestic standard.This result shows that so slight top layer damage can control according to embossed pattern.
About impact property, find that the moulding material of comparative example 1 and 2 preparations has weak cold behavior, in case carry out the high speed impact experiment brittle rupture takes place promptly therefore.The performance of comparative example 1 and 2 moulding materials means when air bag launches according to laser scribing, it may launch in the mode that departs from laser scribing, owing to directly impact, on the surface of skin-material, form serious crack, or the passenger is suffered damage by the fragment of moulding material.In contrast to this, find to have enough low glass transformation temperature (Tg), therefore do not cause problem as the skin-material of comparative example 1 and 2 according to the skin-material of the embodiment of the invention 1 and comparative example's 3 preparations.
Usually, the dashboard of automobile is exposed under the sunlight of relatively large amount than miscellaneous part, causes the temperature of automotive interior to be given birth to suddenly.So the automotive interior temperature rises sharply and causes the change of high molecular weight molecules structure, therefore causes their degraded.In this point, the thermotolerance of dashboard is one of them of the most important weather resistance factor of decision car mass.
The general standards of chromatic aberration of ratifying in automotive industry is that Δ E value is less than 3.All skin-materials that discovery prepares in embodiment 1 and comparative example 1～4 all satisfy Δ E value less than 3.
Particularly in comparative example 4, the table of discovery layer material satisfies standard Δ E value reluctantly.In this case, with the polyurethane(s) pad attach to skin-material, the color change of skin-material, it is different from the skin-material that does not contain the polyurethane(s) liner.When using polyvinyl chloride as skin-material, polyvinyl chloride and the amino reaction that at high temperature comes from the migration of polyurethane(s) liner cause to increase yellow phenomenon rapidly.On the contrary, at the skin-material of comparative example 3 and embodiment 1 preparation according to the present invention, finding seldom has colour-change, shows the rare etiolation that is caused by the amino migration.
In fast light situation, in the skin-material of embodiment 1 and comparative example's preparation, find to have the pattern of similar The above results.
As mentioned above, for weight saving, texture, make air bag evenly inflation and possible utilization again, the moulding material of the thermoplastic polyurethanes of being made up of ether-containing polyester polyol that comprises according to the present invention shows that as dashboard be ideal.
Industrial Applicability A
As mentioned above, skin-material of the present invention is effectively when production has the moulding material of improving production quality, and for example designs flexible, embossing quality and texture; Weather resistance is scrape resistant, heat-proof aging, fast light and chemical resistant properties for example; And security feature for example anti-fog performance, flame retardant properties and air bag is evenly inflated.
The present invention is described in the mode of explanation.According to above-mentioned instruction, the present invention can have many modifications and variation.Therefore, should understand within the scope of the appended claims, the present invention can other modes except that above-mentioned specific descriptions implement.
Claims (5)
1. the thermoplastic polyurethanes that comprises ether-containing polyester polyol, it is by mixing one or more isocyanate compounds of 15～60 weight parts of condensation then, one or more chain extension agents of the ether-containing polyester polyol of 30～70 weight parts and 5～40 weight parts and preparing, wherein said isocyanate compound is selected from diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and dicyclohexyl methane diisocyanate (H12MDI), described chain extension agent is selected from polyvalent alcohol, its example of enumerating is an ethylene glycol, glycol ether, butyleneglycol or hexylene glycol, trivalent alcohol is TriMethylolPropane(TMP) and poly-butyl ether glycol for example, the mixture that obtains of condensation then
Wherein ether-containing polyester polyol prepares as follows: mix one or more polyfunctional group carrier acid of 40～80 weight parts, the poly-butyl ether glycol of 20～100 weight parts, make the mixture reaction that obtains then, the hydroxyl value that obtains thus is 224.11～11.22mgKOH/g, the described carrier acid diacid of selecting oneself, pimelic acid, suberic acid, nonane diacid, sebacic acid, dodecanedioic acid and trimer acid, described poly-butyl ether glycol contains one or more polyfunctional group alkylol cpds, the hydroxyl value that has is 561.0～56.1mgKOH/g, be selected from glycol, the example of enumerating is an ethylene glycol, butyleneglycol or hexylene glycol and trivalent alcohol be TriMethylolPropane(TMP) for example.
2. a method for preparing the thermoplastic polyurethanes that comprises ether-containing polyester polyol comprises the steps:
Mainly be the ether-containing polyester polyol that mixes 30～70 weight parts as claimed in claim 1, the chain propagation agent of 5～40 weight parts, stir 1～10 minute to prepare first mixture down at 30～100 ℃;
The isocyanic ester of 15～60 weight parts is added in first mixture, mix the mixture that obtains subsequently, simultaneously 300～1,100rpm stirs 1～10 minute to prepare second mixture down;
In 60～140 ℃ of following slaking second mixtures 1～48 hour;
Be lower than the reactant that efflorescence obtains from maturation stage under 0 ℃ the temperature; And
Under 150～300 ℃, extrude the atomizing mixture.
3. a moulding material contains the ether-containing polyester polyol just like claim 1 or 2, and the hydroxyl value that has is 221.11～11.22mgKOH/g.
4. moulding material as claimed in claim 3, wherein moulding material is as the skin-material of automobile inner part.
5. as each moulding material of claim 1,2 or 4, wherein moulding material is by efflorescence and extrudes particle or the pellet form that modification obtains.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR2001/62458 | 2001-10-10 | ||
| KR1020010062458A KR100351742B1 (en) | 2001-10-10 | 2001-10-10 | Molded article comprising thermoplastic polyurethane consisting of ether-containing polyester polyol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1492889A true CN1492889A (en) | 2004-04-28 |
| CN1238396C CN1238396C (en) | 2006-01-25 |
Family
ID=36599663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018229336A Expired - Lifetime CN1238396C (en) | 2001-10-10 | 2001-11-30 | Molded material comprising thermoplastic polyurethane consisting of ether-containing polyester polyol and method thereof and product therethrough |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20040116646A1 (en) |
| KR (1) | KR100351742B1 (en) |
| CN (1) | CN1238396C (en) |
| DE (1) | DE10197221B4 (en) |
| WO (1) | WO2003031491A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274977B (en) * | 2007-03-29 | 2011-05-25 | 周建明 | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof |
| CN102459386A (en) * | 2009-05-27 | 2012-05-16 | Sika技术股份公司 | Silane-functional polyesters in moisture-curing compositions based on silane-functional polymers |
| CN103373266A (en) * | 2012-04-11 | 2013-10-30 | 圣州企业股份有限公司 | Automotive pedal pad structure |
| CN104890584A (en) * | 2014-03-05 | 2015-09-09 | 现代摩比斯株式会社 | Crash pad for vehicles and method for manufacturing the same |
| CN109313408A (en) * | 2016-06-30 | 2019-02-05 | 住友理工株式会社 | Electronic photographing device cleaning blade |
| CN111423559A (en) * | 2019-01-08 | 2020-07-17 | 现代摩比斯株式会社 | Composition for automobile interior skin and method for manufacturing same |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100493231B1 (en) * | 2002-07-23 | 2005-06-03 | 현대모비스 주식회사 | The composition for improving the anti-scratching property tpu for instrument of panel |
| KR100568130B1 (en) * | 2003-09-08 | 2006-04-05 | 현대모비스 주식회사 | Mold utilizing hollow tube for forming form |
| KR100631792B1 (en) * | 2004-07-19 | 2006-10-09 | 호성케멕스 주식회사 | Method for producing antistatic polyurethane gloves using aqueous polyurethane emulsion composition |
| KR100674798B1 (en) * | 2005-06-15 | 2007-01-29 | 현대모비스 주식회사 | A composition for manufacturing a thermoplastic polyurethane elastomer by using a Powder Slush Molding Process |
| KR100708712B1 (en) * | 2005-08-27 | 2007-04-17 | 삼성에스디아이 주식회사 | Apparatus for driving plasma display panel and method for driving the same |
| WO2008059796A1 (en) * | 2006-11-17 | 2008-05-22 | Mitsui Chemicals, Inc. | Optical polyurethane resin composition and optical polyurethane resin |
| KR101151055B1 (en) | 2009-11-26 | 2012-06-01 | 덕양산업 주식회사 | Composition for manufacturing a thermoplasticpolyurethane elastomer by using a micro-pellet slush molding process and method using the same |
| KR101306611B1 (en) * | 2011-01-25 | 2013-09-11 | 주식회사 동성하이켐 | Thermoplastic polyurethane elastomer composition for vacuum forming and a method for preparing thereof |
| TWI646125B (en) | 2014-01-06 | 2019-01-01 | 盧森堡商英威達技術有限公司 | Copolyether ester polyol process |
| KR101784442B1 (en) | 2015-07-27 | 2017-11-06 | 주식회사 동성코퍼레이션 | Thermoplastic Polyurethane Resin Composition For T-die Extrusion Molding, Method For Preparing The Same and Molded Product Thereof |
| KR101745116B1 (en) * | 2015-07-27 | 2017-06-08 | 현대자동차주식회사 | Thermoplastic polyurethane composition for injection molding and manufacturing method thereof |
| KR20170109902A (en) * | 2016-03-22 | 2017-10-10 | 현대자동차주식회사 | Thermoplastic polyurethane resin composition enhanced texture and durability and producing method thereof |
| KR20210039689A (en) * | 2019-10-02 | 2021-04-12 | 현대모비스 주식회사 | Crash pad for vehicle and manufacturing method thereof |
Family Cites Families (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4182898A (en) * | 1978-01-20 | 1980-01-08 | Anderson Development Company | Stable and storable polyester-polyether co-prepolymers |
| JPS57111311A (en) * | 1980-12-29 | 1982-07-10 | Nippon Polyurethan Kogyo Kk | Thermoplastic polyurethane resin |
| US4420602A (en) * | 1982-09-27 | 1983-12-13 | The Upjohn Company | Melt-polymerization process for the preparation of thermoplastic polyamides and polyesteramides |
| US4442282A (en) * | 1983-06-20 | 1984-04-10 | The B. F. Goodrich Company | Polyurethane covered golf balls |
| US4634633A (en) * | 1983-12-15 | 1987-01-06 | Sony Corporation | Magnetic recording medium |
| DE3437915A1 (en) * | 1984-10-17 | 1986-04-17 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF POLYETHERESTER POLYOLS, CORRESPONDING PROCESS PRODUCTS AND THEIR USE |
| US4876149A (en) * | 1986-07-31 | 1989-10-24 | Minnesota Mining And Manufacturing Company | Magnetic recording media and a method using a stable fluid reactive dispersion in preparing magnetic recording media |
| DE3716479A1 (en) * | 1987-05-16 | 1988-11-24 | Elastogran Gmbh | METHOD FOR PRODUCING COATINGS FROM POLYURETHANE SINGLE-COMPONENT SYSTEMS AND WATER VAPOR |
| DE69127162T2 (en) * | 1990-05-28 | 1998-02-12 | Teijin Ltd | UPHOLSTERY MATERIAL AND ITS PRODUCTION |
| DE4143454C2 (en) * | 1991-07-01 | 1995-01-05 | Fuller H B Licensing Financ | Process for producing a water vapor permeable material and such a material |
| DE69228606T2 (en) * | 1991-07-03 | 1999-06-24 | Kanebo, Ltd., Tokio/Tokyo | METHOD AND DEVICE FOR PRODUCING A THERMOPLASTIC POLYURETHANE ELASTOMER |
| US5519094A (en) * | 1992-03-06 | 1996-05-21 | B. F. Goodrich Company | Fiber-reinforced thermoplastic molding compositions using a modified thermoplastic polyurethane |
| JP2960820B2 (en) * | 1992-07-16 | 1999-10-12 | 帝人株式会社 | Method of filling fiber assembly, method of manufacturing molded cushion body, and apparatus therefor |
| DE4237915A1 (en) * | 1992-11-10 | 1994-05-11 | Mohndruck Reinhard Mohn Ohg | Desalinated offset printing plate washing water - has a defined sodium content |
| JPH0710955A (en) * | 1993-06-24 | 1995-01-13 | Polyurethan Kasei Kk | Production of rigid polyurethane foam |
| US6033501A (en) * | 1995-07-04 | 2000-03-07 | Teijin Limited | Process for preparing cushioning structure using fiber assembly and apparatus therefor |
| WO1997023670A1 (en) * | 1995-12-25 | 1997-07-03 | Teijin Limited | Heat-bondable conjugated fiber and high-modulus fiber globoid made thereof |
| JP3920930B2 (en) * | 1997-03-27 | 2007-05-30 | 協和発酵ケミカル株式会社 | Polyurethane and polyester polyol |
| FR2779149B1 (en) * | 1998-05-29 | 2000-09-15 | Witco | PROCESS FOR PRODUCING POLYURETHANE FOAM, POLYESTER POLYOL AMINE USED IN THIS PROCESS AND FOAM OBTAINED |
| JP4132244B2 (en) * | 1998-07-06 | 2008-08-13 | 株式会社クラレ | Polyurethane elastic fiber comprising thermoplastic polyurethane and method for producing the same |
| JP3327840B2 (en) * | 1998-07-06 | 2002-09-24 | 三洋化成工業株式会社 | Polyurethane resin slush molding materials |
| DE19961941A1 (en) * | 1999-12-22 | 2001-07-05 | Henkel Kgaa | Polyurethane compositions based on polyether copolymers |
| US6423810B1 (en) * | 2001-02-05 | 2002-07-23 | Lord Corporation | High strength, long-open time structural polyurethane adhesive and method of use thereof |
| JP2005507033A (en) * | 2001-09-28 | 2005-03-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Heterogeneous composite yarn, its cloth and manufacturing method |
| DE60227390D1 (en) * | 2001-09-28 | 2008-08-14 | Invista Tech Sarl | DEHNIBRABLE NON-MATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
-
2001
- 2001-10-10 KR KR1020010062458A patent/KR100351742B1/en active IP Right Grant
- 2001-11-30 US US10/467,056 patent/US20040116646A1/en not_active Abandoned
- 2001-11-30 WO PCT/KR2001/002074 patent/WO2003031491A1/en not_active Application Discontinuation
- 2001-11-30 DE DE10197221T patent/DE10197221B4/en not_active Expired - Lifetime
- 2001-11-30 CN CNB018229336A patent/CN1238396C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274977B (en) * | 2007-03-29 | 2011-05-25 | 周建明 | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof |
| CN102459386A (en) * | 2009-05-27 | 2012-05-16 | Sika技术股份公司 | Silane-functional polyesters in moisture-curing compositions based on silane-functional polymers |
| CN103373266A (en) * | 2012-04-11 | 2013-10-30 | 圣州企业股份有限公司 | Automotive pedal pad structure |
| CN104890584A (en) * | 2014-03-05 | 2015-09-09 | 现代摩比斯株式会社 | Crash pad for vehicles and method for manufacturing the same |
| CN109313408A (en) * | 2016-06-30 | 2019-02-05 | 住友理工株式会社 | Electronic photographing device cleaning blade |
| CN109313408B (en) * | 2016-06-30 | 2021-08-27 | 住友理工株式会社 | Cleaning blade for electrophotographic apparatus |
| CN111423559A (en) * | 2019-01-08 | 2020-07-17 | 现代摩比斯株式会社 | Composition for automobile interior skin and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040116646A1 (en) | 2004-06-17 |
| DE10197221T5 (en) | 2004-04-22 |
| DE10197221B4 (en) | 2006-07-13 |
| KR100351742B1 (en) | 2002-09-05 |
| WO2003031491A1 (en) | 2003-04-17 |
| CN1238396C (en) | 2006-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1238396C (en) | Molded material comprising thermoplastic polyurethane consisting of ether-containing polyester polyol and method thereof and product therethrough | |
| CN106397720B (en) | Thermoplastic polyurethane composition for injection molding, method of manufacturing the same, and articles made therefrom | |
| CN1443215A (en) | Foamed thermoplastic polyurethanes | |
| CN102575036B (en) | Improved adhesion between thermoplastics and polyurethanes | |
| KR101130955B1 (en) | Resin powder composition for slush molding and molded articles | |
| CN1128831C (en) | Use of polyol mixtures in rigid and semi rigid polyurethane foams | |
| CN102216389A (en) | Thermoplastic polyurethane copolymer molding compositions | |
| CN110564276A (en) | Bi-component polyurea coating and application thereof | |
| US20160376410A1 (en) | Powder slush molding composition | |
| CN100360350C (en) | Composite skin for instrument panel and other parts of vehicle passenger compartment, method for making same, and composition for preparing same and method for producing it | |
| CN1271105C (en) | Thermoplastic polyurethanes based on aliphatic isocyanates | |
| WO2010089902A1 (en) | Use of a peba copolymer, composition, process and skin | |
| CN1283209A (en) | Aliphatic, Low-emission thermoplastic polyurethane moulding material suitable for sintering | |
| CN108299668B (en) | Low-odor plastic-spraying-molded automobile instrument board material and preparation method thereof | |
| KR102339304B1 (en) | Thermoplastic polyurethane composition for automobile interior skin and method of manufaturing thereof | |
| US20070228595A1 (en) | Instrument panel comprising a layer of a thermoplastic copolyester elastomer composition | |
| CN111909354B (en) | Waterborne polyurethane resin and preparation method and application thereof | |
| CN115260941B (en) | Dirt-resistant leather product for automotive interiors and preparation method thereof | |
| TW201629114A (en) | Thermoplastic polyurethane composition | |
| CN109689747A (en) | Multi-layer composite materials material products and its method including coating and PC/ABS layers | |
| CN107216436B (en) | Thermoplastic polyurethane resin composition having enhanced texture and durability and method for manufacturing the same | |
| KR100508655B1 (en) | Thermoplastic polyurethane epidermal material consisting of polyester polyol including ether and method for producing the thermoplastic polyurethane epidermal material, and form utilizing the material | |
| KR100508658B1 (en) | Process for the preparation of the powder of thermoplastic polyurethane containing polyester polyol with ether and production therefrom | |
| KR100508654B1 (en) | Thermoplastic polyurethane epidermal material consisting of polyester polyol including ether and method for producing the thermoplastic polyurethane epidermal material, and form utilizing the material | |
| KR100508657B1 (en) | Aliphatic thermoplastic polyurethane epidermal material consisting of polyester polyol including ether and method for producing the alipahtic thermoplastic polyurethane epidermal material, and form utilizing the material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060125 |
|
| CX01 | Expiry of patent term |